CAS: Ambient Electrochemical Activation of Light Alkanes with Early Transition Metal-Oxo Species

CAS：利用早期过渡金属-氧代物质对轻质烷烃进行环境电化学活化

• 批准号: 1955836
• 负责人: Chong Liu
• 金额: $ 45万
• 依托单位: University of California-Los Angeles
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-08-01 至 2023-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1955836&HistoricalAwards=false
• 关键词: CAS; Ambient; Electrochemical; Activation; Light

The abundant, yet widely geographically distributed, natural gas and oil resources in North America have dramatically changed the United States energy portfolio. Conversion of natural gas to useful products relies on high temperature and high pressure processes at centralized locations. Transportation of natural gas from remote sources to these central locations is often not economical. As a result, natural gas is often discarded by flaring at the well, while the oil is recovered. Natural gas, which is mostly methane, and its flaring product, carbon dioxide, are both potent greenhouse gases. Development of catalytic processes that convert natural gas into economically-transportable liquids at these well sites is very desirable. In this project, Professor Chong Liu of the University of California, Los Angeles is developing a new approach using electricity to convert light alkanes, including methane, into liquid products. Dr. Liu is studying new electrochemical catalysts and investigating the fundamental mechanisms of these reactions. Dr. Liu is actively engaged in outreach and education activities to promote engagement of students in science, technology, engineering and mathematics (STEM) disciplines. These activities include the introduction of chemistry topics to local gardeners and farmers in the Los Angeles area as well as undergraduate advising for general chemistry courses assisted by machine learning.With the funding from the Chemical Catalysis Program of the Division of Chemistry, Dr. Liu of the University of California, Los Angeles is developing a mechanistic understanding of how early transition metal-oxo species break the carbon-hydrogen bond in methane during the catalysis. A variety of electrochemical techniques in conjunction with in situ characterizations (including X-ray absorption spectroscopy) are employed to identify important transient intermediate species and determine reaction kinetics with the assistance of first-principle calculations. Also under investigation is the exploration of other molecular and materials catalysts for electrochemical conversion of light alkanes under ambient conditions. Dr. Liu takes soil samples and analyzes their composition for local gardeners and farmers, assisting the local community to develop sustainable agriculture and gardening practices. Dr. Liu is also developing a machine-learning-based platform to develop teaching strategies in general chemistry courses, to advise students on course enrollment, and, in the long run, to establish an online advising program for career development.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

北美大量但广泛的地理分布，天然气和石油资源已极大地改变了美国的能源投资组合。天然气向有用产品的转化取决于集中位置的高温和高压过程。天然气从偏远来源运输到这些中心地点通常不经济。结果，在油回收时，通常会因在油井上爆炸而丢弃天然气。天然气主要是甲烷，其燃烧的产品二氧化碳都是有效的温室气体。将天然气转化为经济转换液体的催化过程在这些井站点是非常可取的。在这个项目中，加利福尼亚大学的Chong Liu教授正在开发一种新方法，使用电力将包括甲烷在内的轻烷烃转化为液体产品。 Liu博士正在研究新的电化学催化剂，并研究了这些反应的基本机制。 Liu博士积极从事宣传和教育活动，以促进学生参与科学，技术，工程和数学（STEM）学科。 These activities include the introduction of chemistry topics to local gardeners and farmers in the Los Angeles area as well as undergraduate advising for general chemistry courses assisted by machine learning.With the funding from the Chemical Catalysis Program of the Division of Chemistry, Dr. Liu of the University of California, Los Angeles is developing a mechanistic understanding of how early transition metal-oxo species break the carbon-hydrogen bond in methane during the catalysis.采用了多种电化学技术以及原位特征（包括X射线吸收光谱）来识别重要的瞬时中间物种，并借助第一原则计算来确定反应动力学。还在研究的是，在环境条件下对轻质烷烃电化学转化的其他分子和材料催化剂的探索。刘博士采集土壤样本并分析其为当地园丁和农民的组成，协助当地社区发展可持续的农业和园艺实践。 Liu博士还正在开发一个基于机器学习的平台，以制定一般化学课程的教学策略，向学生提供课程入学率的建议，从长远来看，以建立一个在线咨询计划的职业发展计划。该奖项反映了NSF的法定任务，并通过评估该基金会的智力功能和广泛的影响来审查NSF的法定任务，并被认为是值得的。

项目成果

Bisulfate as a redox-active ligand in vanadium-based electrocatalysis for CH 4 functionalization

硫酸氢盐作为钒基电催化 CH 4 功能化的氧化还原活性配体

• DOI: 10.1039/d1cc06596c
• 发表时间: 2022
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Xiang, Danlei;Lin, Sheng-Chih;Deng, Jiao;Chen, Hao Ming;Liu, Chong
• 通讯作者: Liu, Chong

Electrocatalytic Methane Functionalization with d 0 Early Transition Metals Under Ambient Conditions

环境条件下 d 0 早期过渡金属的电催化甲烷功能化

• DOI: 10.1002/anie.202107720
• 发表时间: 2021
• 期刊: Angewandte Chemie International Edition
• 作者: Deng, Jiao;Lin, Sheng‐Chih;Fuller, III, Jack T.;Zandkarimi, Borna;Chen, Hao Ming;Alexandrova, Anastassia N.;Liu, Chong
• 通讯作者: Liu, Chong

Ambient methane functionalization initiated by electrochemical oxidation of a vanadium (V)-oxo dimer

• DOI: 10.1038/s41467-020-17494-w
• 发表时间: 2020-07
• 期刊: Nature Communications
• 影响因子: 16.6
• 作者: Jiao Deng;Sheng-Chih Lin;Jack T Fuller;Jesus A. Iñiguez;Danlei Xiang;Di Yang;Gary Chan;Hao Ming Che

Ag II ‐Mediated Electrocatalytic Ambient CH 4 Functionalization Inspired by HSAB Theory

Ag II — 受 HSAB 理论启发的介导电催化环境 CH 4 功能化

• DOI: 10.1002/anie.202104217
• 发表时间: 2021
• 期刊: Angewandte Chemie International Edition
• 作者: Xiang, Danlei;Iñiguez, Jesus A.;Deng, Jiao;Guan, Xun;Martinez, Antonio;Liu, Chong
• 通讯作者: Liu, Chong